Process for producing granular fertilizers



Nov.y 8, 1938.l y H. A.- BEEKHUls, JR l 25136069 PRocEss FOR PRoDUcING GBANULAR FERTLIz'ERs l Filed June 5, l934' Powdered y g Jac/n Fan B7Y I ATTORNEY fpfenfdNe 8i 1938 'y i l 2,136,069

umriss) :STATES PATENT ori-ICE PBQCESS FOB PBODUCING GRANULAR FERTILIZERS A. Beekhuis, Jr., Petersburg, Va., assignor, by mesne assignments, to The Solvay Process Company, New York, N. Y., a corporation of New York Application June5, 1934, Serial lNo. '129,087v 1o claims. (el. 'zr-6o) This application is a. continuation iny part of formed, thegranules are mixed with finely dimy copendlng United States application, Serial vided linert solid material which is preferably No. 521,482, filed March 10, 1931. the same inert solid as was incorporated in the This invention relates to a process for the fused mixture from which the granules were preparation of granular, non-caking fertilizers prepared. The mixture of granules and solid 6 from fusible materials such as ammonium nitrate rinert material is maintained at a Itempera-ture at which are hygroscopic and, when in ordinary which the exterior of the granules softens sufcrystalline form, exhibit a marked tendency to ilciently for the finely divided solid to` adhere absorb moisture from the air vand to cake tothereto and form a surface coating on the granlo gether. The invention further relates to the ules. After receiving a coating of the finely di- 10 granular products obtained from the process vided inert solid, the granules may then be cooled herein described. and are ready for packaging and storage or shipit has heretofore been proposed to prepare a ment. The presence of moisturein the granules mixture of fused ammonium nitrate andfinely -.during treatment with the finely divided inert divided calcium carbonate and to disperse the solid facilitates the formation of the desired ll mixture at a temperature at which it is relatively coating. Accordingly, in the Preferred embodiuid in the form of droplets into a cooling gas to ment of this invention the original fused mixture solidify the material in the form of small grancontains some Water. so that the granules formed ules. While the granular product thus obtained therefrom contain above about .25% moisture.

is much more satisfactory for use as a fertilizer The granules containing this proportion of mois- 20 than ammonium nitrate alone, since the granules ture are treated with the finely divided inert solid of ammonium nitrate-calcium carbonate exhibit and are dried S0 that the iinel C'Jeted PrOdllet a less tendency to cake, nevertheless this comcontains below about 25% moisture. The position is not entirely satisfactory for storage amOllht 0f rieiy divided inert Solid Which may be during prolonged periods of time since, when exapplied t0 the granules aS eOtiD'g may be Varied 25 posed to an atmosphere of relatively high humid-y Within relatively Wide limitslIII general, the ity, it absorbs moisture and cakes together to Va granules should be mixed with about 2% or more considerable degree so as vfrequently to require 0f their Weight of the finely divided inert lmamechanical disintegration before it may be disterial. The amount of solid retained as a coating tributed in the neld. upon the granules may' amount to about 1% or 30 'I'he present invention has for objects, among mOre. and preferably t0 ebOllt 5% 0f the total others, the provision of a novel granular fertl- Weight of the coated material. Under some cirlizer product which has a relatively low hygrocumstances it is desirable that the proportion of scopicity and exhibits a remarkable resistance to finely divided material forming the coating on caring when stored for long periods of tiie at the granules should amount to substantially .35 ordinary atmospheric conditions, and the promore than that indicated above. vision of processes for preparing these fertilizer The product Of this inventiOn Will consist 0f a products. mass of discrete granules which, when fractured,

In carrying out the'process of this invention. a will vshow an interior body constituting the large 40 mixture of a fertilizer material such as ammoniproportion of the total in which the nely divided 40 um nitrate and' a finely divided inert solid such solid material is substantially uniformly diS- as calcium carbonate heated to a temperature at persed throughout /a mass 0f the ammonium hi- Which the ammonium nitrate is fused, is comtrate or other originally fused material which minuted and cooled to form solid granular parhas become solidified from the fused state.

tlcles. The comminution may precede or fol- About this central mass of the granules there low the solidiiication of the fused mixture. Thus. will be observed a relatively thin surface layer the fused mixture may be dispersed as droplets or Coating Containing e much `higher proportion into a cooling gas and the droplets solidified in of the solid finely divided inert material. Some the form of small \pebbles. Ifdesired, the fused 0f this finely divided material 0f the Coating iS mixture may be cooled as, for example, in the imbedded in the outer portions of material which 50 form of a thin layer on the surface of a rotating is solidified from the fused state and another drum from which the solidified material may portion will be found firmly adhering to the sur-v then be lifted by scrapers and broken into fiakes. 'face of this solidiiied fusion. `In whatever manner the solid granules of` am- The following examples' are illustrative of the monium nitrate and calcium carbonate are processes and products of this invention. 'I'he 65 accompanying drawing illustrates one type of apparatus suitable for carrying out the invention, particularly by the procedure described in Example I below.

Example I.A 90% ammonium nitrate solution is heated to a temperature of 100 to 105 C. and nely divided calcium carbonate is mixed with the fused ammonium nitrate in the proportions of about pounds of the calcium carbonate to every 100 pounds of the ammonium nitrate solution. The mixture is stirred to maintain the calcium carbonate in suspension in the fused ammonium nitrate and, at lthe above temperature of 100 to 105 C., is dispersed into a cooling gas in the form of more or less spherical particles. With reference to the accompanying drawing, the mixture of ammonium nitrate and calcium carbonate in a vessel I is maintained at a temperature of 100 to 105 C. and flows at that temperature from vessel I to a rotating disc 2 from which it is dispersed into the air as a cooling gas. These spherical particles are allowed to fall through the cooling gas for such a distance that they are suiiciently solidified to retain their shape upon being collected and passed into a rotary drier by means of collecting hopper 3, the walls of which direct the collected particles to a pipe 4 through which they pass into a pipe 6 leading into a drier 1. The thus solidied matel'ial will contain about 50% ammonium nitrate, about 45% calcium carbonate, and about 5% moisture coming from the water in the ammonium nitrate solution used in making up the fused mixture.

Simultaneously with the feeding of the granules into the rotary drier there is also fed into the drier about 2% of the weight of the granules of finely divided calcium carbonate, such as pulverized limestone by means of a screw conveyor 8 which is fed with the pulverized limestone from a hopper 9. In the rotary drier the granules are agitated and treated with air heated by means of a steam coil I0 and drawn through the drier by means of suction fan II, which serves to dry the granules while they are mixed with the finely divided calcium carbonate until the materialcontains not more than about 0.25% moisture. The air may be introduced into the drier at a temperature of from 50 to 120 C. The finely divided calcium carbonate may be fed to the rotary drier by suspending it in the air passed into the drier employing the apparatus .shown in the drawing. It is preferable, f

however, to feed the calcium carbonate into the drier simultaneously with and at the same end of the drier to which the moist granular material isfed since by so doing the finely divided calcium carbonate and moist granules are mixed in mass and an increased proportion of the calcium carbonate adheres to and coats the granules.f In thus operating, instead of the screw conveyor 8 being positioned at the air intake end of the drier as shown in the drawing, the end of this conveyor is positioned to discharge into pipe Iiso that the nely divided calcium carbonate travels into the drier with the pebbles coming from collecting hopper 3. Under such conditions most of the calcium carbonate adheres to the granules in the drier to form a surface coating thereon. The small amount of the finely divided material, which is carried out of the drier with the air, may be recovered as, for example, in a dust precipitator I2. Any dust thus recovered may be returned to the process for mixture with ammonium nitrate and more limestone in preparing the granulated product by spray cooling a melt of the mixture. In thus treating granules of ammonium nitrate-calcium carbonate with finely divided calcium carbonate, a pebbled product having a materially lessened tendency to cake during storage, is obtained than a similar product not coated as in the foregoing process. The addition of the finely divided calcium carbonate to the material in the drier also has an added advantage in that the pebbled material fed to the drier has a tendency to adhere to the walls of the drier and to form relatively large lumps. This tendency of the material to cake during drying and to adhere to the sides of the drier is substantially completely overcome by introducing calcium carbonate into the drier at the same time that the granules are passed thereinto.

Example II.-A mixture of ammonium nitrate solution and nely divided calcium carf bonate in the proportions of about 150 pounds of calcium carbonate to every pounds of ammonium nitrate solution is heated and pebbled at a temperature of about 100 to 105 C. as

' in the process of Example I. The solidified pebbled particles are passed into a rotary drier Where they are mixed with finely divided calcium .carbonate and treated with warm air to coat and dry the particles.

Example IIL-A melt of ammonium nitrate containing about 95% ammonium nitrate and 5% water is mixed at a temperature of' about C. with powdered limestone. The limestone ,at atmospheric temperatures is introduced into the ammonium nitrate melt in the proportions of about 43 parts of limestone to about 47 parts of ammonium nitrate, calculated on the basis of anhydrous ammonium nitrate. After mixing the foregoing materials, the mixture having a temperature in the'neighborhood of 110 C. is distributed in a thin layer on a cooled rotating drum and the solidified material removed from the drum surface by means of a scraper which breaks the material into akes. The granules of flaked material are passed directly into a rotary drier and treated with heated air until they contain about 0.4% moisture. The thus partially dried granules are then introduced into a rotating drum together with about half their weight of finely powdered limestone. The mixture of granules and limestone is tumbled in the drum at -ing of solidified fusions of mixtures of fusible fertilizer materials other than ammonium nitrate with other nely divided solid inert materials than calcium carbonate, such as pulverized dolomite, finely divided sand, pulverized marl or oyster shells which exhibit a marked tendency to absorb moisture and cake during storage. For example, fertilizers employing urea instead of ammonium nitrate may be prepared in accordance with this invention. Thus, a mixture of molten urea, containing about 95% urea l .the granules are heated while being mixed with ithe, -flnely divided solid. In general, therefore. r.fathe conditions of temperature and moisture con- 55 ,tent ofthe (granules treated with the solid in accordance with thisinvention is such that adesired amount of solid is retained on the granules ,isaoce and water, with ground limestone in the proportions of about 55 parts of limestone for every 45 parts of urea. may be prepared and solidified in the form of solid granules. These granules may bepartially dried so as to leave about 0.4% moisture in them and the granules may then be introduced into a rotating druml together with about hali their weight of iinely powdered limestone. The mixture of granules and limestone is tumbled in the drum at a temperature of about 100 C. to give the granules a coating of limestone. The mixture of granules and excess limestone next passes to a second rotary drier where, by means of heated air, the moisture content is Vreduced to about 0.1%. 'I'he granules arey separated from the excess limestone by screening, and the fines may be returned for mixture with urea in preparing additional material for granulation. Under the specified conditions, the limestone forms a substantially uniform, adherent coating on the surfaces of the granules. This coating ofthe granules with finely divided limestone improves the storage properties of the granules. This is believed due to the tendency of the urea to migrate to the surface of the gran- `ules during their drying treatment. By applying the coating to the granules the tendency of any surface layer of urea to cause the caking of the granules during storage is repressed.

When calcium carbonate is employed as the inert solid material in preparing the fertilizers of this invention, it may be in the form of puiverized limestone or precipitated calcium 'carbonate. Calcium carbonate or dolomite, however, are preferred to materials such as sand, since they act not only to reduce the caking of the material of the mixture but also, when ineluded in a fertilizer, 'act as a soil conditioner.

In coating the granulesof material with limestone or other nely divided -solid inert material, the surface of granules .while agitated with the solid material should be sumciently'plastic so that the solid is bound to the granules prior to the drying and the coat is firmly retained by crystallization of some ammonium nitrate in the coat. The plasticity of the granule surface increases as the temperature of the granules is raised or as their moisture content is increased. The portion of solid retained as a coating on the product, accordingly, varies with the moisture content and with the temperature at which as 'asurface coating. In' general, this may be accomplished by treating granules containing ,fromy 10.1%v to 1% moisture with the solid `at temperatures of 90 C. to 120 C, or by treating granules 4containing an increased proportion of moisture* at' correspondingly. lower temperatures.

jwhile a product of improved characteristics results when the granules are coated with an amount voi' the finely divided solid corresponding vention, it is intended that all matter contained in the above description shall' be interpreted as illustrative and not in a limiting sense. .The fertilizer product described may be admixed with other ingredients if desired or may be applied alone to the soil.

I claim: l. The process for preparingv fertilizers which comprises forming a mixture of ammonium nitrate and an inert finely divided solid material containing a small proportion of moisture into granules, mixing said. granules with iinely divided inert solid material and drying the mix` ture of granules and inert solid material while heating it to a temperature at which the exl5 von the granules an adhering surface coating of terior of the granules softens and there is formed said granules containing more than 0.25% liiiin ture, agitating the resulting mixture at e. temperature at whichthe exterior of the granules softens and there is formed an adhering coating ofy inert solid material on said granules, and drying the granules prior to` discontinuing agitating them with the inert finely divided solid material. 4

3. In a process wherein a granular aonium nitrate-calcium carbonate fertiiizer containing moisture is prepared, that improvement which comprises mixing with the granules of said fertilizer containing more than .25% moisturenely divided calcium carbonate, heating said mixture while agitating it to a temperature at which the exterior of the granules softens and a portion of said finely divided calcium carbonate becomes imbedded inthe outer portions of the granules and another portion adheres to the surface thereof and during the heating of the mixture drying it until the moisture content of the granules is reduced to below .25% and a firmly adhering surface coating of said finely divided calcium carbonate is formed on said granules.

t. The process for preparing granular fertilizers which comprises heating a mixture oi ammonium nitrate, an inert finely divided solid material, and water to a temperature at which a fluid melt containing said inert solid material dispersed throughout a fusion of said ammonium y nitrate is formed, commuting and solidifying the melt to form granules, mixing the granules while they still contain above .25% moisture with about 2% or more of a nely divided inert solid material and heating the mixture of granules 'and inert solid material to a vtemperature at which the exterior of the granules softens while drying the mixture until the moisture content of the granules is reduced to below .25% and there is formed on the granules an adhering surface coating of said last mentioned inert solid material.

5. In a process for producing a fertilizer in which moist granules comprising an intimate mixture of ammonium nitrate and an inert solid are treated with heated air to droy the granules. the improvement which comprises treating said moist granules with heated air carrying finely divided solid material in suspension therein while agitating the granules to prevent them from sticking together.

6. The process of producing a granular fertilizer which comprises preparing a iiuid mixture containing ammonium nitrate and an inert solid in finely divided form, dispersing said fluid mixturein the form of separate particles and solidifying said particles by means of a cooling gas, and treating the solidified particles with heated air carrying in suspension a quantity of said inert solid in a nely divided form.

7. The process of producing a granular fertilizer which comprises preparing a uid mixture containing ammonium nitrate and an inert solid in nely divided form, dispersing said fluid mixture lin the form of separate particles and solidifying said particles by means f a cooling gas, and treating the solidified particles with a hot gas carrying in suspension a quantity of inert solid in a finely divided form.

8. The process of producing a granular fertilizer which comprises preparing a fluid mixture #of ammonium nitrate and nely divided calcium carbonate, dispersing said fluid mixture in the form of separate particles into a cooling gas, solidfying said particles during their travel through Said gas, passing said solidied particles in countercurrent flow with air heated to a temperature of 50 to 120 C. prior to introduction of the same into contact with said particles,

and introducing into said air prior to its contact with the solidified material calcium carbonate dust.

9. The process of producing a granular fertilizer which comprises preparing a iiuid mixture containing ammonium nitrate and an inert solid in nely divided form, dispersing said fluid mixture in the form of separate particles into a cooling gas, solidifying said particles duringtheir travel through said gas, and treating the solidiiied particles with heated air carrying calcium carbonate dust in suspension therein.

10. The process of producing a granular fertilizer which comprises preparing a iiuid mixture containing ammonium nitrate and finely divided calcium carbonate, dispersing said fluid mixture in the form of separate particles into a cooling gas, solidifying said particles during their travel through said gas, and treating the solidified particles with heated air carrying calcium carbonate dust in suspension therein.

HERMAN A. BEEKHUIS, JR. 

